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SUMMARY
GENERAL CLASSIFICATION OF ANALYTICAL TECHNIQUES
SPECTROSCOPIC TECHNIQUES
Atomic Spectroscopy
AAS
AES
Molecular Spectroscopy
XRF
UV-Vis
Luminescence
FT-IR
FT- Raman
REFERENCES
1
2c
m1
m2
k
The change in vibration must stimulate changes in the dipole moment of the bonds
present in a molecule. Thus not all vibrations are IR active.
2.
The frequency of the radiation must satisfy the energy difference between each
vibrational level
level, ii.e.
e the incident energy should be quantized (E = hv) to exert the
transition between two vibrational levels.
v=3
Average b
A
bond
d llength
th
increases
v=2
v=1
hv
v=0
3.
The selection rule is that always v = 1 is allowed and stronger. Other transitions such
as v = 2,
2 3
3, etc., though
h
h not allowed
ll
d (f
(forbidden),
bidd ) may occur as weaker
k transitions.
ii
4.
The excitation from the ground state v0 to the first excited state v1 is the most likely
transition and is called fundamental transition ((v = 1).
) These are veryy strong
g when
compared to other transitions such as v0 = v2 (v = 2), or v0 = v3 (v = 3), which are called
as overtone transitions.
Asymmetric
Bending
Scissoring Rocking Wagging Twisting
+
+
+
The sign +
+ indicates the movement towards the view point and - indicates away from that
that.
The energy associated with stretching vibrations are higher than the bending vibrations
and normally observed in higher wavenumber region of the IR spectrum.
Scissoring:
g
Symmetric: s
Rocking:
Asymmetric: as
Wagging:
Twisting:
For a molecule containing more than two atoms all the vibrations shown may be possible.
However for bigger molecules which may contain several types of atoms and bonds, the
multitude of possible vibrations is complex.
REPRESENTATION OF IR SPECTRUM
Units, Range and Representation of IR Spectra:
IR spectra are normally given in wavenumber (v) against percentage transmittance (%T). The
wavenumber expression is taken because of the convenience that it is directly proportional
to energy.
Wavenumber (v) = 1/ (cm)
100%
%T
1 eV = 1.602 10-19 J
0%
4000cm1
400cm1
Near IR
10,000
4000
Mid IR
Far IR
200
10 cm-1
IR SPECTRAL INTERPRETATION
IR SPECTRAL CHART (stretching)
Type of Compound
Wavenumber Range, cm-1
Bond
CC
C-C
Alkanes
1000 - 1040
C=C
Alkenes
1610 - 1680
C=C
Aromatic rings
1500 - 1600
CC
C
C
Alkynes
2100 - 2260
C-N
Amines, Amides
1180 - 1360
CN
Nitriles
2210 - 2280
C-O
1050 - 1300
C=O
1690 - 1760
C-H
Aldehydes
2700 - 2900
C-H
Alkanes
2850 - 2970
C-H
Alkenes
3000 - 3095
C-H
Alkynes
3300
C-H
Aromatic rings
3010 - 3100
NH
N-H
A i
Amines,
Amides
A id
3300 - 3500
O-H
3590 - 3650
3200 - 3600
3500 - 3650
2500 - 3000
C-F (1000 - 1150cm-1) > C-Cl (700 - 800cm-1 ) > C-Br (600 - 700cm-1) > C-I (500 - 600cm-1)
IR SPECTRAL INTERPRETATION
IR SPECTRAL CHART ((bending/deformation)
g
)
Type of Compound
Alkanes:
CH3 (deformation)
CH2 (scissoring)
CH2 (wagging)
CH2 (twisting)
CH2 (rocking)
1470 (as),
) 1380 (s)
1465
1180-1350
1300
720
Alkenes:
=C-H (ip deformation)
=C-H (oop deformation)
1400
600-1000
Alkynes:
C-H (ip deformation)
C-H (oop deformation)
620-730
580-700
Aromatic ring:
=C-H (ip deformation)
=C-H (oop deformation)
1000-1275
690-900
ip in plane
oop- out of plane
background
4.5
4.0
Res
sponse
3.5
3.0
2.5
??
2.0
??
1.5
1.0
05
0.5
0.0
7500
7000
6500
6000
5500
5000
4500
4000 3500
Wavenumber
3000
2500
2000
1500
1000
500
Unprocessed spectrum:
Finger Print
Note that the Y-axis is given as %Transmittance: the transmittance can be related to
absorbance as follows:
IR SPECTRA INSTRUMENTATION
Instrumentation: The older double beam technique which is known as dispersive IR spectrometer
has been outdated.
outdated Instead the latest equipment is referred as Fourier Transform-Infra
Transform Infra Red (FT(FT
IR) spectrometer which utilises a single beam of un-dispersed IR radiation which is passed through
the sample and the absorptions at all wavelengths are received at the detector simultaneously.
A computerized mathematical manipulation (known as Fourier Transform) is performed to obtain
absorption data for each and every wavelength. To perform this type of calculation periodic
interference of light pattern is required. This is accomplished by splitting the IR beam into two using
a beam splitter and reconstructing the split beam again by a combination of two mirrors, one fixed
and another moveable. The following is the simplified version of the instrument:
Fixed Mirror
Movable Mirror
IR Beam
Sample
Compartment
Detector
FT-IR Spectrometers
IR SPECTRA APPLICATIONS
Applications: It finds extensive use in the identification and structural analysis of organic
compounds, natural products, polymers, etc. The presence of particular functional group in a
given organic compound can be easily identified. With the finger print region a new compound
can be identified, as no two compounds can have the same spectral characteristics at this region.
There are various modes of measurements other than transmission as follow:
Specular reflectance (for thin films, reflective substrates)
Diffuse reflectance (for powders)
Attenuated total reflectance (ATR) (for strong absorbing substances)
Photo-acoustic detector (for strong absorbing substances, depth profiling)
IR-Microscope
IR
Microscope (for direct Identification of impurities and micro
micro-sampled
sampled substances).
Disadvantages:
- Samples containing mixture of substances can not be analysed.
- Solid sample processing and liquid sample handling are time consuming.
- For mid-IR range the beam splitter and window materials for holding organic liquids are made of
KBr or NaCl which are highly
g y hygroscopic.
yg
p
- For every range the source, beam splitter and detector need to be changed.
Transmission
Absorbance
Specular
Grazing Angle
Reflection
Others
External
Internal
DRIFTS
ATR
PAS
Transmission
Microscopy
Reflection
ATR
RetroReflection
Grazing
g
Angle
IR SPECTRA Example
Dehydration
D
h d ti off cyclohexanol
l h
l ((a)) tto 1
1-cyclohexene
l h
(b)
(b), note
t th
the di
disappearance off O H
-1
band at ~3500 cm and appearance of C = C band at ~1600 cm-1 for (b)
1
1.
CH3
CH3
CH3 CH2 O
CH3
O
C
CH3
OH
2
2.
OH
3.
OH
OH
OH
OH
Intra-molecular
Intra
molecular H
H-bonding
bonding exists and O H band appears
at ~3000 cm-1
No intra-molecular
intra molecular H
H-bonding
bonding and O H band
appears at ~3500 cm-1
4
4.
CH3
OH
5.
(CH3CH2)2NH
N H band appears at 3300 3500 cm-1
CH3
OC2H5
(CH3CH2)3N
No N H band
FTIR-ATR
N
Si
Cl
Cl Cl
p p
peptide
bond
OTS
Traansmittan
nce (%))
ethylenediamine
IgG
1645,1550
peptide bond
4000
3500
3000
2500
2000
1732, HC=O
1500
-1
Wavenumbers (cm )
C.-Y. Xue, K.-L Yang, Langmuir, 23 (10), 5831, 2007.